Method for synthesizing dissymmetric sulfoether

ABSTRACT

A method for synthesizing dissymmetric sulfoether includes the following step: a) under the condition of tetrabutylammonium halide catalysis, compounds having a structure of formula (I), compounds having a structure of formula (II) and salts having sulfur and oxygen are reacted in a solvent to give dissymmetric sulfoether having a structure of formula (III).

The present application claims priority to Chinese patent applicationNo. 201610423506.2, titled “Method for Synthesizing DissymmetricSulfoether”, filed with the Chinese State Intellectual Property Officeon Jun. 15, 2016, the entire contents of which are incorporated hereinby reference.

FIELD

The present application relates to the field of organic chemistry, andmore particularly to a synthetic method of dissymmetric sulfoether.

BACKGROUND

Dissymmetric sulfoether is a kind of important sulfur-containingcompounds. It is not only widely found in natural products,pharmaceutically active molecules, but also acts as advanced materialsand metal ligands, or as important organic synthesis intermediates.

Dissymmetric sulfoether compounds have a wide range of applications inbiomedicine, for example:

Methionine is one of the essential amino acids in the human body, and itparticipates in protein synthesis. Because it can not be generated bythe body itself, it must be obtained from the outside. Lack ofmethionine will lead to inhibition of protein synthesis in vivo, causingdamage to the body. At present, methionine is usually synthesized by thecoupling reaction of halide and thiol and its related derivatives underthe catalysis of transition metal.

Cilastatin is a thiamycin antibiotic with carbapenem ring, which is acommercially available antimicrobial agent prepared by semi-synthesis ofthiamycin from culture medium of S. cattleya. Cilastatin is used forsepsis caused by sensitive organism, infective endocarditis,osteomyelitis, arthritis, skin and soft tissue infections. At present,Cilastatin is synthesized by direct addition of thiol and its relatedderivatives to unsaturated compounds under the condition with transitionmetal or no metal.

Cinanserin can be used to treat psychiatric disorders. At present,Cinanserin is usually synthesized by addition of thiol and its relatedderivatives to alkynes under the condition of transition metal catalyst.

It can be seen that thiol compounds, which are highly toxic, malodorous,sensitive and perishable, are inevitably used in the reaction process ofthe current method for synthesizing dissymmetric sulfoether in additionto the need for expensive metal catalyst and harsh reaction conditions(anhydrous, anaerobic, etc.). These shortcomings seriously restrict thepractical use of the method. Therefore, the development of novelsynthetic methods for dissymmetric sulfoether compounds has been a hotresearch field in organic chemistry and pharmaceutical chemistry.

SUMMARY

In view of the above, it is an object of the present application toprovide a method for synthesizing dissymmetric sulfoether. The methodprovided by the present application has a mild reaction condition and isenvironment-friendly.

A method for synthesizing dissymmetric sulfoether is provided in thepresent application, comprising the following step:

a) under the condition of tetrabutylammonium halide catalysis, thecompounds having a structure of formula (I), the compounds having astructure of formula (II) and salts having sulfur and oxygen are reactedin a solvent to give dissymmetric sulfoether having a structure offormula (III);

wherein, R₁ is selected from phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R₂ is selectedfrom hydrogen, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, thienyl or substituted thienyl; or R₁, R₂ form fluorene ringor thioxanthone ring with the C to which it is attached;

R₃ is selected from hydrogen or alkyl;

R₄ is selected from hydrogen, phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R₅ is selectedfrom hydrogen; or R₄, R₅ form fluorene ring or thioxanthone ring withthe C to which it is attached;

R₆ is selected from alkyl or substituted alkyl;

X is selected from Cl, Br or I;

said salts having sulfur and oxygen include sodium thiosulfate and/orsodium sulfite.

Preferably, R₁ is selected from phenyl, C1˜C5 alkyl-substituted phenyl,C1˜C5 alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl,C1˜C5 alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl,halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl,C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl.

Preferably, R₂ is selected from hydrogen, phenyl, C1˜C5alkyl-substituted phenyl, C1˜C5 alkoxy-substituted phenyl,halogen-substituted phenyl, naphthyl, C1˜C5 alkyl-substituted naphthyl,C1˜C5 alkoxy-substituted naphthyl, halogen-substituted naphthyl,thienyl, C1˜C5 alkyl-substituted thienyl, C1˜C5 alkoxy-substitutedthienyl or halogen-substituted thienyl.

Preferably, R₃ is selected from hydrogen and C1˜C5 alkyl.

Preferably, R₄ is selected from hydrogen, phenyl, C1˜C5alkyl-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5alkyl-substituted naphthyl, halogen-substituted naphthyl, thienyl, C1˜C5alkyl-substituted thienyl or halogen-substituted thienyl.

Preferably, R₆ is selected from C1˜C30 alkyl, cyano-substituted C1˜C20alkyl, cyano-substituted C1˜C20 benzyl, C1˜C5 alkyl-substituted benzyl,halogen-substituted benzyl, fluorenyl and any one of the structuralsubstituents represented in formulas (a-1)˜(a-9):

In formulas (a-3)˜(a-9), m₁, m₂, m₃, n, q, p₁, p₂, r₁, r₂ and e areintegers from 0 to 5, respectively.

Preferably, said structural compound of formula (I) is1,1-diphenylpropyl-2-enyl-1-ol, 1,1-bis (4-fluorophenyl)prop-2-enyl-1-ol, 1,1-bis (4-chlorophenyl) prop-2-enyl-1-ol, 1,1-bis(4-bromophenyl) prop-2-enyl-1-ol, 1,1-bis (4-methylphenyl)prop-2-enyl-1-ol, 1,1-bis (4-methoxyphenyl) prop-2-enyl-1-ol,1-phenyl-1-p-methylphenyl-2-en-1-ol,1-(3,4-dimethylphenyl)-1-phenylprop-2-enyl-1-ol,1-phenyl-1-p-bromophenyl-2-enyl-1-ol,1-phenyl-1-o-fluorophenylprop-2-enyl-1-ol,1-(naphthalen-2-yl)-1-phenylprop-2-enyl-1-ol,2-methyl-1,1-diphenylprop-2-enyl-1-ol, 9-alkenyl-9H-fluorenyl-9-ol,9-alkenyl-9H-thioxanthen-9-ol, 1-phenylprop-2-enyl-1-ol,(E)-1,3-diphenylprop-2-enyl-1-ol, (E)-1,3-bis (4-fluorophenyl)prop-2-enyl-1-ol, (E)-1,3-bis (4-chlorophenyl) prop-2-enyl-1-ol,(E)-1,3-bis (4-bromophenyl) prop-2-enyl-1-ol, (E)-1,3-bis(naphthalen-2-yl) prop-2-enyl-1-ol, (E)-1,3-bis (thiophen-2-yl)prop-2-enyl-1-ol or (E)-2-methyl-1,3-diphenylprop-2-enyl-1-ol.

Preferably, said structural compound of formula (II) is p-cyanobenzylchloride, m-cyanobenzyl chloride, p-trifluoromethylbenzyl chloride,o-bromobenzyl chloride, p-methylbenzyl bromide, 9-bromofluorene,(4-(chloromethyl) phenyl) (1H-indol-1-yl) methanone, ((3 aR, 5S, 5aS,8aS, 8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo [4,5-b:4′,5′-d] pyran-5-yl) methyl 4-(chloromethyl) phenyl ester,chloroacetonitrile, 1-bromoacetoacetate, 2-bromo-N,N-diethylpropionamide, bromopropyne, (3-chloropropyl-1-ynyl) benzene,ethyl 4-bromocrotonate, geranyl bromide, iodine iodobutane, and iodinen-decane, 4-chlorobutyronitrile or ethyl 4-bromobutyrate.

Preferably, molar ratio of structural compounds of formula(I):structural compounds of formula (II):salts having sulfur and oxygenis 1:(1.5˜3):(2˜4).

Preferably, temperature of said reaction is 20˜90° C.

Preferably, time of said reaction is 3˜8 h.

Preferably, in step a), after the completion of reaction of structuralcompounds of formula (I), structural compounds of formula (II) and saltshaving sulfur and oxygen, extraction, drying and column chromatographyare performed successively to give dissymmetric sulfoether having astructure represented in formula (III).

Preferably, said solvent is water.

Compared with the prior art, the present application provides a methodfor synthesizing dissymmetric sulfoether. The method provided in thepresent application comprises the following step a) under the conditionof tetrabutylammonium halide catalysis, the compounds having a structureof formula (I), the compounds having a structure of formula (II) andsalts having sulfur and oxygen are reacted in a solvent to givedissymmetric sulfoether having a structure of formula (III).

Wherein R₁ is selected from phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R₂ is selectedfrom hydrogen, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, thienyl or substituted thienyl; or R₁, R₂ form fluorene ringor thioxanthone ring with the C to which it is attached; R₃ is selectedfrom hydrogen or alkyl; R₄ is selected from hydrogen, phenyl,substituted phenyl, naphthyl, substituted naphthyl, thienyl orsubstituted thienyl; R₅ is selected from hydrogen; or R₄, R₅ formfluorene ring or thioxanthone ring with the C to which it is attached;R₆ is selected from alkyl or substituted alkyl; X is selected from Cl,Br or I; said salts having sulfur and oxygen include sodium thiosulfateand/or sodium sulfite. In the method provided in the presentapplication, substituted aryl allyl alcohol compounds, substituted alkylhalides and salts having sulfur and oxygen are used as the reaction rawmaterials and tetrabutylammonium halide as a catalyst, using one-potmethod to prepare dissymmetric sulfoether. In this method, the rawmaterials are cheap and easy to obtain, the catalytic conditions aresimple, mild and without the participation of transition metals, and theyield is relatively high. In addition, in the preferred embodiment ofthe present application, the reaction is carried out in the aqueousphase, meeting the green chemistry requirements. The results ofexperiments show that the method provided by the present application cansynthesize a series of dissymmetric sulfoether with potential biologicaland pharmacological activity, and the highest product yield is more than91%.

DETAILED DESCRIPTION OF THE EMBODIMENTS

The technical solution in the embodiments of the present applicationwill be described below clearly and completely. Obviously, the describedembodiments are merely part of the present invention, and not allembodiments. All other embodiments obtained by those of ordinary skillin the art based on embodiments in the present application withoutmaking creative work are within the scope of the present invention.

A method for synthesizing dissymmetric sulfoether is provided in thepresent application, comprising the following step:

a) under the condition of tetrabutylammonium halide catalysis, thecompounds having a structure of formula (I), the compounds having astructure of formula (II) and salts having sulfur and oxygen are reactedin a solvent to give dissymmetric sulfoether having a structure offormula (III);

wherein, R₁ is selected from phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R₂ is selectedfrom hydrogen, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, thienyl or substituted thienyl; or R₁, R₂ form a fluorene ringor thioxanthone ring with the C to which it is attached;

R₃ is selected from hydrogen or alkyl;

R₄ is selected from hydrogen, phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R₅ is selectedfrom hydrogen; or R₄, R₅ form a fluorene ring or thioxanthone ring withthe C to which it is attached;

R₆ is selected from alkyl or substituted alkyl;

X is selected from Cl, Br or I;

said salts having sulfur and oxygen include sodium thiosulfate and/orsodium sulfite.

In the synthetic method provided by the present application, thecompounds having a structure of formula (I), the compounds having astructure of formula (II) and salts having sulfur and oxygen are reactedin a solvent with tetrabutylammonium halide catalysis. Wherein, thestructure of said structural compound in formula (I) is as below:

In formula (I), R₁ is selected from phenyl, substituted phenyl,naphthyl, substituted naphthyl, thienyl or substituted thienyl;preferably, it is selected from phenyl, C1˜C5 alkyl-substituted phenyl,C1˜C5 alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl,C1˜C5 alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl,halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl,C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl; morepreferably, it is selected from phenyl, fluorophenyl, chlorophenyl,bromophenyl, methylphenyl, dimethylphenyl, methoxyphenyl, naphthyl orthienyl; most preferably, it is selected from phenyl, 4-fluorophenyl,o-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, p-bromophenyl,4-methylphenyl, p-methylphenyl, 3,4-dimethylphenyl, 4-methoxyphenyl,naphthalen-2-yl or thiophen-2-yl; R₂ is selected from hydrogen, phenyl,substituted phenyl, naphthyl, substituted naphthyl, thienyl orsubstituted thienyl; preferably, it is selected from hydrogen, phenyl,C1˜C5 alkyl-substituted phenyl, C1˜C5 alkoxy-substituted phenyl,halogen-substituted phenyl, naphthyl, C1˜C5 alkyl-substituted naphthyl,C1˜C5 alkoxy-substituted naphthyl, halogen-substituted naphthyl,thienyl, C1˜C5 alkyl-substituted thienyl, C1˜C5 alkoxy-substitutedthienyl or halogen-substituted thienyl; more preferably, it is selectedfrom hydrogen, phenyl, fluorophenyl, chlorophenyl, bromophenyl,methylphenyl, dimethylphenyl, methoxyphenyl, naphthyl or thienyl; mostpreferably, it is selected from hydrogen, phenyl, 4-fluorophenyl,o-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, p-bromophenyl,4-methylphenyl, p-methylphenyl, 3,4-dimethylphenyl, 4-methoxyphenyl,naphthalen-2-yl or thiophen-2-yl. Or R₁, R₂ form a fluorene ring orthioxanthone ring with the C to which it is attached.

In formula (I), R₃ is selected from hydrogen or alkyl, preferably fromhydrogen, C1˜C5 alkyl, more preferably from hydrogen, methyl or ethyl.

In formula (I), R₄ is selected from hydrogen, phenyl, substitutedphenyl, naphthyl, substituted naphthyl, thienyl or substituted thienyl;preferably, it is selected from hydrogen, phenyl, C1˜C5alkyl-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5alkyl-substituted naphthyl, halogen-substituted naphthyl,halogen-substituted thienyl, C1˜C5 alkyl-substituted thienyl orhalogen-substituted thienyl; more preferably, it is selected fromhydrogen, phenyl, fluorophenyl, chlorophenyl, bromophenyl, naphthyl orthienyl; most preferably, it is selected from hydrogen, phenyl,4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl or naphthalen-2-yl orthiophen-2-yl. R₅ is selected from hydrogen. Or R₄, R₅ form a fluorenering or thioxanthone ring with the C to which it is attached.

In one embodiment provided in the present application, said structuralcompound of formula (I) is 1,1-diphenylpropyl-2-enyl-1-ol (1), 1,1-bis(4-fluorophenyl) prop-2-enyl-1-ol (2), 1,1-bis (4-chlorophenyl)prop-2-enyl-1-ol (3), 1,1-bis (4-bromophenyl) prop-2-enyl-1-ol (4),1,1-bis (4-methylphenyl) prop-2-enyl-1-ol (5), 1,1-bis (4-methoxyphenyl) prop-2-enyl-1-ol (6), 1-phenyl-1-p-methylphenyl-2-en-1-ol(7), 1-(3,4-dimethylphenyl)-1-phenylprop-2-enyl-1-ol (8),1-phenyl-1-p-bromophenyl-2-enyl-1-ol (9),1-phenyl-1-o-fluorophenylprop-2-enyl-1-ol (10),1-(naphthalen-2-yl)-1-phenylprop-2-enyl-1-ol (11),2-methyl-1,1-diphenylprop-2-enyl-1-ol (12), 9-alkenyl-9H-fluorenyl-9-ol(13), 9-alkenyl-9H-thioxanthen-9-ol (14), 1-phenylprop-2-enyl-1-ol (15),(E)-1,3-diphenylprop-2-enyl-1-ol (16), (E)-1,3-bis (4-fluorophenyl)prop-2-enyl-1-ol (17), (E)-1,3-bis (4-chlorophenyl) prop-2-enyl-1-ol(18), (E)-1,3-bis (4-bromophenyl) prop-2-enyl-1-ol (19), (E)-1,3-bis(naphthalen-2-yl) prop-2-enyl-1-ol (20), (E)-1,3-bis (thiophen-2-yl)prop-2-enyl-1-ol (21) or (E)-2-methyl-1,3-diphenylprop-2-enyl-1-ol (22).In the present application, the specific structures of the structuralcompound (I) having a structures of formulas (1)˜(22) are as below:

In formulas (1)˜(10), for the name of corresponding numbering compound,R¹ can be selected from hydrogen, fluorine, chlorine, bromine, methyl,methoxy or dimethyl; R² can be selected from hydrogen, fluorine,chlorine, bromine, methyl, methoxy or dimethyl. In formulas (16)˜(19),for the name of corresponding numbering compound, R¹ can be selectedfrom hydrogen, fluorine, chlorine or bromine; R² can be selected fromhydrogen, fluorine, chlorine or bromine.

In the present application, structure of said structural compounds offormula (II) is as below:

In formula (II), R₆ is selected from alkyl or substituted alkyl;preferably, it is selected from C1˜C30 alkyl, cyano-substituted C1˜C20alkyl, benzyl, C1˜C5 alkyl-substituted benzyl, halogen-substitutedbenzyl, fluorenyl or any of the structural substituents of formulas(a-1)˜(a-9):

In formulas (a-3)˜(a-9), m₁, m₂, m₃, n, q, p₁, p₂, r₁, r₂ and e areintegers from 0 to 5, respectively.

In one embodiment provided in the present application, said structuralcompound of formula (II) is p-cyanobenzyl chloride (23), m-cyanobenzylchloride (24), p-trifluoromethylbenzyl chloride (25), o-bromobenzylchloride (26), p-methylbenzyl bromide (27), 9-bromofluorene (28),(4-(chloromethyl) phenyl) (1H-1-indolyl) methanone (29), ((3aR, 5S, 5aS,8aS, 8bR)-2,2,7,7-tetramethyltetrahydroxy-3 aH-bis [1,3] dioxo [4,5-b:4′,5′-d] 5-pyranyl) methyl 4-(chloromethyl) phenyl ester (30),chloroacetonitrile (31), 1-bromoacetoacetate (32), 2-bromo-N,N-diethylpropionamide (33), bromopropyne (34), (3-chloropropyl-1-ynyl)benzene (35), ethyl 4-bromocrotonate (36), geranyl bromide (37), iodineiodobutane (38), iodine n-decane (39), 4-chlorobutyronitrile (40) orethyl 4-bromobutyrate (41). In the present application, structures ofsaid structural compounds of formula (II) having structures of formulas(23)˜(41) are as below:

In formulas (23)˜(27), for the name of corresponding numbering compound,R can be selected from cyano, trifluoromethyl, bromo or methyl; X can beselected from chlorine or bromine.

In the present application, said salts having sulfur and oxygen includesodium thiosulfate and/or sodium sulfite, preferably sodium thiosulfate;said solvent is preferably water. Said molar ratio of structuralcompound of formula (I):structural compound of formula (II):salt havingsulfur and oxygen is preferably 1:(1.5˜3):(2˜4), more preferably1:(1.5˜2.4):(2˜4), even more preferably 1:(1.5˜2):(2˜2.4), mostpreferably 1:2:2.4. Said molar ratio of tetrabutylammonium halide tostructural compound of formula (I) is preferably (0.01˜1):1, morepreferably (0.1˜0.5):1, most preferably 0.2:1. Said usage ratio ofsolvent to structural compound of formula (I) is preferably (0.1˜10)mL:(0.1˜0.5) mmol, more preferably (0.5˜2) mL:(0.1˜0.5) mmol, mostpreferably 1 mL:0.3 mmol.

In the present application, during the reaction procedure of structuralcompound of formula (I), structural compound of formula (II), salthaving sulfur and oxygen, said reaction is preferably carried out underconfined conditions; temperature of said reaction is preferably 20˜90°C., more preferably 25˜80° C., even more preferably 70˜80° C., mostpreferably 80° C.; time of said reaction is preferably 3˜8 h, morepreferably 5˜6 h. After the completion of reaction, reaction solution isobtained and said reaction solution is subjected to extraction, dryingand column chromatography, respectively. Herein, extractant used in saidextraction is preferably ethyl acetate; desiccant used in said drying ispreferably anhydrous sodium sulfate; stationary phase used in saidcolumn chromatography is preferably 300˜400 mesh silica gel powder;mobile phase of said column chromatography is preferably ethyl acetateand petroleum ether. After the completion of column chromatography,dissymmetric sulfoether having a structure of formula (III) areobtained:

In formula (III), the selection ranges of R₁˜R₆ are consistent withthose of formulas (I) and (II), and are not described again here.

In the method provided in the present application, substituted arylallyl alcohol compounds, substituted alkyl halides and salts havingsulfur and oxygen are used as the reaction raw materials andtetrabutylammonium halide as a catalyst, using one-pot method to preparedissymmetric sulfoether. In this method, the raw materials are cheap andeasy to obtain, the catalytic conditions are simple, mild and withoutthe participation of transition metals, and the yield is relativelyhigh. In addition, in the preferred embodiment of the presentapplication, the reaction is carried out in the aqueous phase, meetingthe green chemistry requirements. The results of experiments show thatthe method provided by the present application can synthesize a seriesof dissymmetric sulfoether with potential biological and pharmacologicalactivity, and the highest product yield is more than 91%.

For a clearer understanding, the present application is described indetail through the following examples.

Example 1 Synthesis of 4-((3,3-diarylablylthio) methyl) benzonitrile

0.3 mmol 1,1-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0778 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.49˜7.42 (m, 2H), 7.38˜7.33 (m, 3H),7.29˜7.25 (m, 3H), 7.22˜7.18 (m, 2H), 7.18˜7.13 (m, 4H), 6.08 (t, J=7.8Hz, 1H), 3.63 (s, 2H), 3.18 (d, J=7.8 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-diaryl allylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 76%.

Example 2 Synthesis of 4-((3,3-bis (4-fluorophenyl) allylthio) methyl)benzonitrile

0.3 mmol 1,1-bis (4-fluorophenyl) prop-2-enyl-1-ol (0.0739 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0932 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.51 (d, J=8.3 Hz, 2H), 7.24 (d, J=8.2 Hz,2H), 7.16˜7.09 (m, 4H), 7.09˜7.03 (m, 2H), 7.00˜6.94 (m, 2H), 6.01 (t,J=7.8 Hz, 1H), 3.65 (s, 2H), 3.14 (d, J=7.9 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-bis (4-fluorophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 82%.

Example 3 Synthesis of 4-((3,3-bis (4-chlorophenyl) allylthio) methyl)benzonitrile

0.3 mmol 1,1-bis (4-chlorophenyl) prop-2-enyl-1-ol (0.0837 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0865 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.56˜7.52 (m, 2H), 7.38˜7.35 (m, 2H),7.29˜7.24 (m, 4H), 7.13˜7.08 (m, 4H), 6.08 (t, J=7.9 Hz, 1H), 3.66 (s,2H), 3.16 (d, J=7.9 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-bis (4-chlorophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 80%.

Example 4 Synthesis of 4-((3,3-bis (4-bromophenyl) allylthio) methyl)benzonitrile

0.3 mmol 1,1-bis (4-bromophenyl) prop-2-enyl-1-ol (0.1104 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.1361 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.54˜7.47 (m, 4H), 7.42˜7.38 (m, 2H), 7.21(d, J=8.3 Hz, 2H), 7.05˜6.99 (m, 4H), 6.07 (t, J=7.9 Hz, 1H), 3.64 (s,2H), 3.12 (d, J=7.9 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-bis (4-bromophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 71%.

Example 5 Synthesis of 4-((3,3-p-tolyl allylthio) methyl) benzonitrile

0.3 mmol 1,1-bis (4-methylphenyl) prop-2-enyl-1-ol (0.0715 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0898 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.45 (d, J=8.3 Hz, 2H), 7.16 (dd, J=7.8, 5.7Hz, 4H), 7.09 (s, 4H), 7.03 (d, J=8.0 Hz, 2H), 6.00 (t, J=7.8 Hz, 1H),3.62 (s, 2H), 3.18 (d, J=7.8 Hz, 2H), 2.41 (s, 3H), 2.33 (s, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-p-tolyl allylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 76%.

Example 6 Synthesis of 4-((3,3-p-methoxyphenyl allylthio) methyl)benzonitrile

0.3 mmol 1,1-bis (4-methoxyphenyl) prop-2-enyl-1-ol (0.0811 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0970 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.50˜7.44 (m, 2H), 7.19 (d, J=8.3 Hz, 2H),7.16˜7.12 (m, 2H), 7.09˜7.04 (m, 2H), 6.90˜6.85 (m, 2H), 6.83˜6.79 (m,2H), 5.93 (t, J=7.8 Hz, 1H), 3.85 (s, 3H), 3.80 (s, 3H), 3.63 (s, 2H),3.18 (d, J=7.8 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3,3-p-methoxyphenyl allylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 60%.

Example 7 Synthesis of 4-((3-phenyl-3-p-tolylthio) methyl) benzonitrile

0.3 mmol 1-phenyl-1-p-methylphenyl-2-en-1-ol (0.0673 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0745 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.45 (d, J=8.1 Hz, 2H), 7.34 (dd, J=4.1, 2.4Hz, 1H), 7.27 (d, J=7.2 Hz, 1H), 7.22˜7.19 (m, 1H), 7.18˜7.13 (m, 3.0Hz, 4H), 7.09 (s, 2H), 7.03 (d, J=8.0 Hz, 1H), 6.09˜6.00 (m, 1H), 3.62(d, J=2.1 Hz, 2H), 3.18 (dd, J=9.1, 7.9 Hz, 2H), 2.41 (s, 1.5H), 2.33(s, 1.5H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3-phenyl-3-p-tolylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 67%.

Example 8 Synthesis of 4-((3-(3,4-dimethylphenyl)-3-phenylallylthio)methyl) benzonitrile

0.3 mmol 1-(3,4-dimethylphenyl)-1-phenylprop-2-enyl-1-ol (0.0715 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0886 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.47˜7.42 (m, 2H), 7.36˜7.32 (m, 1.8H),7.28˜7.26 (m, 1.2H), 7.24˜7.20 (m, 1H), 7.18˜7.09 (m, 3.2H), 7.04 (d,J=7.8 Hz, 0.7H), 6.98 (s, 0.5H), 6.93˜6.86 (m, 1.5H), 6.02 (t, J=7.8 Hz,1H), 3.62 (d, J=3.3 Hz, 2H), 3.18 (dd, J=12.1, 7.8 Hz, 2H), 2.31 (s,1.5H), 2.24 (d, J=4.3 Hz, 3H), 2.22 (s, 1.5H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of4-((3-(3,4-dimethylphenyl)-3-phenylallylthio) methyl) benzonitrile(purity>95%); the product yield was calculated and the result was 79%.

Example 9 Synthesis of 4-((3-phenyl-3-p-bromophenylthio) methyl)benzonitrile

0.3 mmol 1-phenyl-1-p-bromophenyl-2-en-1-ol (0.0868 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0840 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.53˜7.44 (m, 3H), 7.41˜7.35 (m, 3H),7.29˜7.26 (m, 1H), 7.22 (d, J=8.3 Hz, 1H), 7.18˜7.11 (m, 3H), 7.08˜7.01(m, 2H), 6.11˜6.03 (m, 1H), 3.63 (d, J=10.7 Hz, 2H), 3.15 (dd, J=7.9,3.6 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3-phenyl-3-p-bromophenylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 67%.

Example 10 Synthesis of 4-((3-phenyl-3-o-fluorophenylthio) methyl)benzonitrile

0.3 mmol 1-phenyl-1-p-bromophenyl-2-en-1-ol (0.0685 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0669 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.48 (d, J=8.2 Hz, 1H), 7.42 (d, J=8.2 Hz,1H), 7.38˜7.26 (m, 4H), 7.23 (d, J=5.0 Hz, 1H), 7.21˜7.17 (m, 1H),7.16˜7.11 (m, 3H), 7.10˜7.01 (m, 2H), 6.22 (t, J=7.7 Hz, 0.45H), 6.02(t, J=7.6 Hz, 0.55H), 3.65 (s, 2H), 3.24 (d, J=7.7 Hz, 1.1H), 3.10 (d,J=7.7 Hz, 0.9H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3-phenyl-3-o-fluorophenylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 62%.

Example 11 Synthesis of 4-((3-(naphthalen-2-yl)-3-phenylallylthio)methyl) benzonitrile

0.3 mmol 1-(naphthalen-2-yl)-1-phenylprop-2-enyl-1-ol (0.0781 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0678 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.93˜7.79 (m, 3H), 7.69 (d, J=8.5 Hz, 0.5H),7.50˜7.40 (m, 3.5H), 7.40˜7.33 (m, 2.5H), 7.32˜7.24 (m, 4.5H), 7.13 (d,J=8.3 Hz, 1.2H), 6.99 (d, J=8.3 Hz, 0.8H), 6.42 (t, J=7.7 Hz, 0.45H),5.96 (t, J=7.8 Hz, 0.55H), 3.71 (s, 1.1H), 3.59˜3.48 (m, 0.9H), 3.40 (d,J=7.8 Hz, 1.1H), 2.94 (d, J=7.7 Hz, 0.9H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((3-(naphthalen-2-yl)-3-phenylallylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 76%.

Example 12 Synthesis of 4-((2-methyl-3,3-diphenylallylthio) methyl)benzonitrile

0.3 mmol 2-methyl-1,1-diphenylprop-2-enyl-1-ol (0.0673 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0806 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.49˜7.44 (m, 2H), 7.30˜7.22 (m, 6H), 7.16(d, J=8.3 Hz, 2H), 7.13˜7.09 (m, 3H), 7.08 (s, 1H), 3.60 (s, 2H), 3.24(s, 2H), 1.89 (s, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((2-methyl-3,3-diphenylallylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 74%.

Example 13 Synthesis of 4-((2-(9H-fluoren-9-ylidene) ethylthio) methyl)benzonitrile

0.3 mmol 9-alkenyl-9H-fluorenyl-9-ol (0.0625 g), 0.6 mmol of cyanobenzylchloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138 g) and 0.06mmol of tetrabutylammonium iodide (0.0222 g) were weighed and placed in20 mL reaction tube. 1 ml water was added to the reaction tube as asolvent, and the tube was sealed. Reaction was carried out with stirringat 80° C. for 5 hours. After completion of the reaction, the reactionsolution was dried by ethyl acetate and anhydrous sodium sulfate andseparated by column chromatography, successively, to yield 0.0593 g ofreaction product. Conditions for column chromatography were: 300˜400mesh silica gel powder as stationary phase, ethyl acetate (A) andpetroleum ether (B) as mobile phase, changing program of mobile phase(A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.73 (d, J=7.5 Hz, 1H), 7.69 (d, J=7.5 Hz,1H), 7.60 (d, J=7.5 Hz, 1H), 7.51 (d, J=7.7 Hz, 1H), 7.45 (d, J=8.2 Hz,2H), 7.40˜7.34 (m, 2H), 7.32˜7.27 (m, 3H), 7.22˜7.16 (m, 1H), 6.61 (t,J=8.2 Hz, 1H), 3.81 (d, J=8.2 Hz, 2H), 3.75 (s, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((2-(9H-fluoren-9-ylidene) ethylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 58%.

Example 14 Synthesis of 4-((2-(9H-thioxanthen-9-yl) ethylthio) methyl)benzonitrile

0.3 mmol 9-alkenyl-9H-thioxanthene-9-ol (0.0721 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0867 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.52˜7.45 (m, 2H), 7.44˜7.40 (m, 1H),7.35˜7.26 (m, 5H), 7.26˜7.23 (m, 1H), 7.20˜7.14 (m, 1H), 7.04 (d, J=8.3Hz, 2H), 5.88 (t, J=7.7 Hz, 1H), 3.53 (s, 2H), 3.35 (d, J=7.7 Hz, 2H)ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-((2-(9H-thioxanthen-9-yl) ethylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 62%.

Example 15 Synthesis of 4-(cinnamylthiomethyl) benzonitrile

0.3 mmol 1-phenylprop-2-enyl-1-ol (0.0403 g), 0.6 mmol of cyanobenzylchloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138 g) and 0.06mmol of tetrabutylammonium iodide (0.0222 g) were weighed and placed in20 mL reaction tube. 1 ml water was added to the reaction tube as asolvent, and the tube was sealed. Reaction was carried out with stirringat 80° C. for 5 hours. After completion of the reaction, the reactionsolution was dried by ethyl acetate and anhydrous sodium sulfate andseparated by column chromatography, successively, to yield 0.0867 g ofreaction product. Conditions for column chromatography were: 300˜400mesh silica gel powder as stationary phase, ethyl acetate (A) andpetroleum ether (B) as mobile phase, changing program of mobile phase(A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.60 (d, J=8.3 Hz, 2H), 7.43 (d, J=8.3 Hz,2H), 7.36-7.29 (m, 4H), 7.28-7.25 (m, 1H), 6.36 (d, J=15.7 Hz, 1H),6.18-6.09 (m, 1H), 3.72 (s, 2H), 3.21 (dd, J=7.3, 0.9 Hz, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of 4-(cinnamylthiomethyl) benzonitrile(purity>95%); the product yield was calculated and the result was 23%.

Example 16 Synthesis of (E)-4-((1,3-diphenylallylthio) methyl)benzonitrile

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofcyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0848 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.60˜7.54 (m, 2H), 7.39 (s, 1H), 7.37˜7.30(m, 8H), 7.29˜7.27 (m, 1H), 7.27˜7.21 (m, 2H), 6.43˜6.32 (m, 2H), 4.44(d, J=7.7 Hz, 1H), 3.75˜3.60 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-diphenylallylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 74%.

Example 17 Synthesis of (E)-4-((1,3-bis (4-fluorophenyl) allylthio)methyl) benzonitrile

0.3 mmol (E)-1,3-bis (4-fluorophenyl) prop-2-enyl-1-ol (0.0739 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0993 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.60 (d, J=8.3 Hz, 2H), 7.38 (d, J=8.2 Hz,2H), 7.35˜7.29 (m, 4H), 7.07˜6.97 (m, 4H), 6.35 (d, J=15.7 Hz, 1H),6.26˜6.19 (m, 1H), 4.41 (d, J=8.4 Hz, 1H), 3.74˜3.61 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-bis (4-fluorophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 91%.

Example 18 Synthesis of (E)-4-((1,3-bis (4-chlorophenyl) allylthio)methyl) benzonitrile

0.3 mmol (E)-1,3-bis (4-chlorophenyl) prop-2-enyl-1-ol (0.0837 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0887 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.60 (d, J=8.2 Hz, 2H), 7.37 (d, J=8.2 Hz,2H), 7.34˜7.25 (m, 8H), 6.41˜6.21 (m, 2H), 4.39 (d, J=7.9 Hz, 1H),3.75˜3.59 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-bis (4-chlorophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 72%.

Example 19 Synthesis of (E)-4-((1,3-bis (4-bromophenyl) allylthio)methyl) benzonitrile

0.3 mmol (E)-1,3-bis (4-bromophenyl) prop-2-enyl-1-ol (0.1104 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.1242 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.62˜7.58 (m, 2H), 7.48˜7.42 (m, 4H), 7.37(d, J=8.3 Hz, 2H), 7.24˜7.18 (m, 4H), 6.35˜6.25 (m, 2H), 4.37 (d, J=7.0Hz, 1H), 3.73˜3.60 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-bis (4-bromophenyl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 83%.

Example 20 Synthesis of (E)-4-((1,3-bis (naphthalen-2-yl) allylthio)methyl) benzonitrile

0.3 mmol (E)-1,3-bis (naphthalen-2-yl) prop-2-enyl-1-ol (0.0931 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0566 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.89˜7.76 (m, 8H), 7.70 (s, 1H), 7.60˜7.54(m, 4H), 7.51˜7.42 (m, 5H), 7.39 (d, J=8.2 Hz, 2H), 6.67˜6.54 (m, 2H),4.68 (d, J=7.3 Hz, 1H), 3.79˜3.63 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-bis (naphthalen-2-yl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 43%.

Example 21 Synthesis of (E)-4-((1,3-bis (thiophen-2-yl) allylthio)methyl) benzonitrile

0.3 mmol (E)-1,3-bis (thiophen-2-yl) prop-2-enyl-1-ol (0.0667 g), 0.6mmol of cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0674 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.60 (d, J=8.3 Hz, 2H), 7.42 (d, J=8.2 Hz,2H), 7.27 (d, J=1.3 Hz, 1H), 7.19 (dd, J=4.6, 1.4 Hz, 1H), 7.01˜6.94 (m,4H), 6.56 (d, J=15.5 Hz, 1H), 6.14 (dd, J=15.5, 8.6 Hz, 1H), 4.67 (d,J=8.6 Hz, 1H), 3.82˜3.70 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((1,3-bis (thiophen-2-yl) allylthio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 60%.

Example 22 Synthesis of (E)-4-((2-methyl-1,3-biphenylalerythio) methyl)benzonitrile

0.3 mmol (E)-2-methyl-1,3-diphenylprop-2-enyl-1-ol (0.0673 g), 0.6 mmolof cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0793 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.59 (d, J=8.2 Hz, 2H), 7.40 (d, J=8.2 Hz,2H), 7.38˜7.30 (m, 8H), 7.27˜7.21 (m, 3H), 6.58 (s, 1H), 4.43 (s, 1H),3.75˜3.63 (m, 2H), 1.82 (d, J=1.1 Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((2-methyl-1,3-biphenylalerythio)methyl) benzonitrile (purity>95%); the product yield was calculated andthe result was 74%.

Example 23 Synthesis of (E)-3-((1,3-diphenylallylthio) methyl)benzonitrile

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofm-cyanobenzyl chloride (0.0910 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0677 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.57˜7.50 (m, 3H), 7.42˜7.38 (m, 2H),7.36˜7.31 (m, 6H), 7.30˜7.21 (m, 3H), 6.46˜6.33 (m, 2H), 4.45 (d, J=7.7Hz, 1H), 3.73˜3.58 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-3-((1,3-diphenylallylthio) methyl)benzonitrile (purity>95%); the product yield was calculated and theresult was 66%.

Example 24 Synthesis of (E)-(1,3-diphenylallyl) (4-(trifluoromethyl)benzyl) sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofp-trifluoromethylbenzyl chloride (0.1167 g), 0.72 mmol of sodiumthiosulfate (0.1138 g) and 0.06 mmol of tetrabutylammonium iodide(0.0222 g) were weighed and placed in 20 mL reaction tube. 1 ml waterwas added to the reaction tube as a solvent, and the tube was sealed.Reaction was carried out with stirring at 80° C. for 5 hours. Aftercompletion of the reaction, the reaction solution was dried by ethylacetate and anhydrous sodium sulfate and separated by columnchromatography, successively, to yield 0.0773 g of reaction product.Conditions for column chromatography were: 300˜400 mesh silica gelpowder as stationary phase, ethyl acetate (A) and petroleum ether (B) asmobile phase, changing program of mobile phase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.63 (d, J=8.0 Hz, 2H), 7.48 (d, J=8.0 Hz,2H), 7.46˜7.38 (m, 7H), 7.37˜7.29 (m, 3H), 6.53˜6.39 (m, 2H), 4.52 (d,J=7.6 Hz, 1H), 3.84˜3.70 (m, 2H). ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(1,3-diphenylallyl) (4-(trifluoromethyl)benzyl) sulfoether (purity>95%); the product yield was calculated andthe result was 67%.

Example 25 Synthesis of (E)-(2-bromobenzyl) (1,3-diphenylallyl)sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofo-bromobenzyl chloride (0.1233 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0868 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=δ 7.54 (dd, J=8.0, 1.3 Hz, 1H), 7.44˜7.40 (m,2H), 7.40˜7.35 (m, 3H), 7.35˜7.27 (m, 5H), 7.27˜7.25 (m, 1H), 7.24˜7.20(m, 1H), 7.13˜7.06 (m, 1H), 6.53˜6.35 (m, 2H), 4.59 (d, J=8.3 Hz, 1H),3.87˜3.73 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(2-bromobenzyl) (1,3-diphenylallyl)sulfoether (purity>95%); the product yield was calculated and the resultwas 73%.

Example 26 Synthesis of (E)-(4-methylbenzyl) (1,3-diphenylallyl)sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofp-methylbenzyl bromide (0.1110 g), 0.72 mmol of sodium thiosulfate(0.1138 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0852 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.41-7.35 (m, 4H), 7.35˜7.25 (m, 5H),7.24˜7.17 (m, 3H), 7.12 (d, J=7.6 Hz, 2H), 6.48-6.34 (m, 2H), 4.45 (d,J=6.8 Hz, 1H), 3.70˜3.57 (m, 2H), 2.34 (s, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(4-methylbenzyl) (1,3-diphenylallyl)sulfoether (purity>95%); the product yield was calculated and the resultwas 86%.

Example 27 Synthesis of (E)-(1,3-diphenylallyl) (9H-fluoren-9-yl)sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of9-bromofluorene (0.1471 g), 0.72 mmol of sodium thiosulfate (0.1138 g)and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighed andplaced in 20 mL reaction tube. 1 ml water was added to the reaction tubeas a solvent, and the tube was sealed. Reaction was carried out withstirring at 80° C. for 5 hours. After completion of the reaction, thereaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0854 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.72˜7.69 (m, 1H), 7.62˜7.57 (m, 2H), 7.51(d, J=7.3 Hz, 1H), 7.38˜7.33 (m, 1H), 7.31 (d, J=1.9 Hz, 1H), 7.30˜7.25(m, 5H), 7.23˜7.19 (m, 1H), 6.94˜6.90 (m, 2H), 6.88˜6.83 (m, 2H),6.00˜5.92 (m, 1H), 5.62 (d, J=15.6 Hz, 1H), 4.93 (s, 1H), 4.17˜4.10 (m,1H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(1,3-diphenylallyl) (9H-fluoren-9-yl)sulfoether (purity>95%); the product yield was calculated and the resultwas 72%.

Example 28 Synthesis of (E)-1-(4-((1,3-diphenylallylthio) methyl)phenyl)-1H-indole

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of(4-(chloromethyl) phenyl) (1H-indol-1-yl) methanone (0.1618 g), 0.72mmol of sodium thiosulfate (0.1138 g) and 0.06 mmol oftetrabutylammonium iodide (0.0222 g) were weighed and placed in 20 mLreaction tube. 1 ml water was added to the reaction tube as a solvent,and the tube was sealed. Reaction was carried out with stirring at 80°C. for 5 hours. After completion of the reaction, the reaction solutionwas dried by ethyl acetate and anhydrous sodium sulfate and separated bycolumn chromatography, successively, to yield 0.0574 g of reactionproduct. Conditions for column chromatography were: 300˜400 mesh silicagel powder as stationary phase, ethyl acetate (A) and petroleum ether(B) as mobile phase, changing program of mobile phase (A:B) from 1:20 to1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=8.40 (d, J=8.2 Hz, 1H), 7.74˜7.67 (m, 2H),7.63˜7.58 (m, 1H), 7.46 (d, J=8.0 Hz, 2H), 7.42˜7.35 (m, 6H), 7.34˜7.26(m, 6H), 7.26 (d, J=1.5 Hz, 1H), 6.62 (d, J=3.8 Hz, 1H), 6.52˜6.34 (m,2H), 4.51 (d, J=7.7 Hz, 1H), 3.82˜3.68 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-1-(4-((1,3-diphenylallylthio) methyl)phenyl)-1H-indole (purity>95%); the product yield was calculated and theresult was 42%.

Example 29 Synthesis of (3aR, 5S, 5aS, 8aS,8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo [4,5-b:4′,5′-d] pyran-5-yl) methyl 4-(((E)-1,3-diphenylallyl thio) methyl)phenyl ester

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of (3aR,5S, 5aS, 8aS, 8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo[4,5-b: 4′,5′-d] pyran-5-yl) methyl 4-(chloromethyl) phenyl ester(0.2477 g), 0.72 mmol of sodium thiosulfate (0.1138 g) and 0.06 mmol oftetrabutylammonium iodide (0.0222 g) were weighed and placed in 20 mLreaction tube. 1 ml water was added to the reaction tube as a solvent,and the tube was sealed. Reaction was carried out with stirring at 80°C. for 5 hours. After completion of the reaction, the reaction solutionwas dried by ethyl acetate and anhydrous sodium sulfate and separated bycolumn chromatography, successively, to yield 0.1227 g of reactionproduct. Conditions for column chromatography were: 300˜400 mesh silicagel powder as stationary phase, ethyl acetate (A) and petroleum ether(B) as mobile phase, changing program of mobile phase (A:B) from 1:20 to1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=8.00 (d, J=8.2 Hz, 2H), 7.37 (d, J=7.9 Hz,6H), 7.34˜7.30 (m, 3H), 7.30˜7.21 (m, 3H), 6.39 (d, J=7.3 Hz, 2H), 5.58(d, J=5.0 Hz, 1H), 4.66 (dd, J=7.9, 2.6 Hz, 1H), 4.54 (dd, J=11.5, 4.9Hz, 1H), 4.44 (dd, J=11.1, 7.3 Hz, 2H), 4.38˜4.32 (m, 2H), 4.22˜4.17 (m,1H), 3.77˜3.61 (m, 2H), 1.53 (s, 3H), 1.49 (s, 3H), 1.36 (s, 3H), 1.34(s, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (3aR, 5S, 5aS, 8aS,8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo [4,5-b:4′,5′-d] pyran-5-yl) methyl 4-(((E)-1,3-diphenylallyl thio) methyl)phenyl ester (purity>95%); the product yield was calculated and theresult was 68%.

Example 30 Synthesis of (E)-2-(1,3-diphenylallyl thio) acetonitrile

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofchloroacetonitrile (0.0453 g), 0.72 mmol of sodium thiosulfate (0.1138g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.1130 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.54˜7.49 (m, 2H), 7.49˜7.43 (m, 2H),7.36˜7.30 (m, 2H), 7.29˜7.24 (m, 2H), 6.58 (d, J=15.6 Hz, 1H), 6.31 (dd,J=15.6, 9.0 Hz, 1H), 4.83 (d, J=8.9 Hz, 1H), 3.31˜3.06 (m, 2H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-2-(1,3-diphenylallyl thio) acetonitrile(purity>95%); the product yield was calculated and the result was 89%.

Example 31 Synthesis of (E)-4-(1,3-diphenylallylthio)-3-oxobutanoate

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of1-bromoacetoacetate (0.0453 g), 0.72 mmol of sodium thiosulfate (0.0988g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighedand placed in 20 mL reaction tube. 1 ml water was added to the reactiontube as a solvent, and the tube was sealed. Reaction was carried outwith stirring at 80° C. for 5 hours. After completion of the reaction,the reaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0901 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.43˜7.38 (m, 4H), 7.37˜7.28 (m, 5H),7.25˜7.21 (m, 1H), 6.56 (d, J=15.7 Hz, 1H), 6.34 (dd, J=15.7, 9.0 Hz,1H), 4.59 (d, J=9.1 Hz, 1H), 4.21˜4.14 (m, 2H), 3.61 (s, 2H), 3.44˜3.27(m, 2H), 1.26 (t, J=7.2 Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-(1,3-diphenylallylthio)-3-oxobutanoate(purity>95%); the product yield was calculated and the result was 85%.

Example 32 Synthesis of (E)-2-(1,3-diphenylallylthio)-N,N-diethylpropionamide

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of2-bromo-N, N-diethylpropionamide (0.1249 g), 0.72 mmol of sodiumthiosulfate (0.0988 g) and 0.06 mmol of tetrabutylammonium iodide(0.0222 g) were weighed and placed in 20 mL reaction tube. 1 ml waterwas added to the reaction tube as a solvent, and the tube was sealed.Reaction was carried out with stirring at 80° C. for 5 hours. Aftercompletion of the reaction, the reaction solution was dried by ethylacetate and anhydrous sodium sulfate and separated by columnchromatography, successively, to yield 0.0692 g of reaction product.Conditions for column chromatography were: 300˜400 mesh silica gelpowder as stationary phase, ethyl acetate (A) and petroleum ether (B) asmobile phase, changing program of mobile phase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.46˜7.40 (m, 2H), 7.40˜7.32 (m, 4H),7.32˜7.26 (m, 3H), 7.25˜7.19 (m, 1H), 6.57˜6.48 (m, 1H), 6.47˜6.38 (m,1H), 4.71 (d, J=8.4 Hz, 1H), 3.62˜3.55 (m, 1H), 3.48˜3.37 (m, 2H),3.35˜3.29 (m, 1H), 3.27˜3.13 (m, 2H), 3.10˜2.94 (m, 1H), 1.57˜1.47 (m,3H), 1.11˜1.04 (m, 3H), 1.00˜0.91 (m, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-2-(1,3-diphenylallylthio)-N,N-diethylpropionamide (purity>95%); the product yield was calculated andthe result was 65%.

Example 33 Synthesis of (E)-(1,3-diphenylallyl) (prop-2-ynyl) sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofbromopropyne (0.0714 g), 0.72 mmol of sodium thiosulfate (0.0988 g) and0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighed andplaced in 20 mL reaction tube. 1 ml water was added to the reaction tubeas a solvent, and the tube was sealed. Reaction was carried out withstirring at 80° C. for 5 hours. After completion of the reaction, thereaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0714 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.48˜7.43 (m, 2H), 7.41˜7.35 (m, 3H),7.34˜7.25 (m, 5H), 6.59 (d, J=15.6 Hz, 1H), 6.39 (dd, J=15.6, 8.9 Hz,1H), 4.87 (d, J=8.9 Hz, 1H), 3.24 (dd, J=16.9, 2.6 Hz, 1H), 3.09 (dd,J=16.9, 2.6 Hz, 1H), 2.30 (t, J=2.6 Hz, 1H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(1,3-diphenylallyl) (prop-2-ynyl)sulfoether (purity>95%); the product yield was calculated and the resultwas 90%.

Example 34 Synthesis of (E)-(1,3-diphenylallyl) (phenylprop-2-ynyl)sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of1-phenyl-3-chloro-1-propyne (0.0904 g), 0.72 mmol of sodium thiosulfate(0.0988 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0669 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.50˜7.44 (m, 4H), 7.42˜7.37 (m, 3H),7.37˜7.35 (m, 1H), 7.35˜7.27 (m, 6H), 7.25˜7.21 (m, 1H), 6.61 (d, J=15.7Hz, 1H), 6.48˜6.39 (m, 1H), 4.93 (d, J=8.8 Hz, 1H), 3.48 (d, J=16.8 Hz,1H), 3.34 (d, J=16.8 Hz, 1H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-(1,3-diphenylallyl) (phenylprop-2-ynyl)sulfoether (purity>95%); the product yield was calculated and the resultwas 66%.

Example 35 Synthesis of (E)-4-((E)-1,3-diphenylallyl thio) but-2-enoicacid ethyl ester

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of ethyl4-bromocrotonate (0.1158 g), 0.72 mmol of sodium thiosulfate (0.0988 g)and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighed andplaced in 20 mL reaction tube. 1 ml water was added to the reaction tubeas a solvent, and the tube was sealed. Reaction was carried out withstirring at 80° C. for 5 hours. After completion of the reaction, thereaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0642 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.43˜7.39 (m, 3H), 7.39˜7.32 (m, 4H),7.31˜7.27 (m, 2H), 7.25˜7.21 (m, 1H), 6.96˜6.89 (m, 1H), 6.48 (d, J=15.7Hz, 1H), 6.36 (dd, J=15.7, 8.6 Hz, 1H), 5.88˜5.81 (m, 1H), 4.57 (d,J=8.6 Hz, 1H), 4.24˜4.17 (m, 2H), 3.29˜3.21 (m, 1H), 3.17˜3.09 (m, 1H),1.30 (t, J=7.1 Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-((E)-1,3-diphenylallyl thio)but-2-enoic acid ethyl ester (purity>95%); the product yield wascalculated and the result was 63%.

Example 36 Synthesis of ((E)-3,7-dimethyloxin-2,6-dienyl)((E)-1,3-diphenylallyl) sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofgeranyl bromide (0.1303 g), 0.72 mmol of sodium thiosulfate (0.0988 g)and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighed andplaced in 20 mL reaction tube. 1 ml water was added to the reaction tubeas a solvent, and the tube was sealed. Reaction was carried out withstirring at 80° C. for 5 hours. After completion of the reaction, thereaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0801 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.43˜7.40 (m, 2H), 7.39˜7.36 (m, 2H),7.35˜7.26 (m, 5H), 7.24˜7.20 (m, 1H), 6.50˜6.36 (m, 2H), 5.31˜5.24 (m,1H), 5.14˜5.07 (m, 1H), 4.60 (d, J=7.5 Hz, 1H), 3.20˜3.12 (m, 1H),3.11˜3.03 (m, 1H), 2.12˜2.00 (m, 4H), 1.69 (s, 3H), 1.62 (s, 3H), 1.57(s, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of ((E)-3,7-dimethyloxin-2,6-dienyl)((E)-1,3-diphenylallyl) sulfoether (purity>95%); the product yield wascalculated and the result was 74%.

Example 37 Synthesis of (E)-tert-butyl (1,3-diphenylallyl) sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofn-butane (0.1104 g), 0.72 mmol of sodium thiosulfate (0.0988 g) and 0.06mmol of tetrabutylammonium iodide (0.0222 g) were weighed and placed in20 mL reaction tube. 1 ml water was added to the reaction tube as asolvent, and the tube was sealed. Reaction was carried out with stirringat 80° C. for 5 hours. After completion of the reaction, the reactionsolution was dried by ethyl acetate and anhydrous sodium sulfate andseparated by column chromatography, successively, to yield 0.0611 g ofreaction product. Conditions for column chromatography were: 300˜400mesh silica gel powder as stationary phase, ethyl acetate (A) andpetroleum ether (B) as mobile phase, changing program of mobile phase(A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.44˜7.37 (m, 4H), 7.36˜7.25 (m, 5H),7.24˜7.20 (m, 1H), 6.49 (d, J=15.7 Hz, 1H), 6.44˜6.34 (m, 1H), 4.59 (d,J=8.4 Hz, 1H), 2.54˜2.42 (m, 2H), 1.61˜1.54 (m, 2H), 1.43˜1.33 (m, 2H),0.88 (t, J=7.3 Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-tert-butyl (1,3-diphenylallyl)sulfoether (purity>95%); the product yield was calculated and the resultwas 72%.

Example 38 Synthesis of (E)-decyl (1,3-diphenylallyl) sulfoether

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol ofn-decane (0.1609 g), 0.72 mmol of sodium thiosulfate (0.0988 g) and 0.06mmol of tetrabutylammonium iodide (0.0222 g) were weighed and placed in20 mL reaction tube. 1 ml water was added to the reaction tube as asolvent, and the tube was sealed. Reaction was carried out with stirringat 80° C. for 5 hours. After completion of the reaction, the reactionsolution was dried by ethyl acetate and anhydrous sodium sulfate andseparated by column chromatography, successively, to yield 0.0869 g ofreaction product. Conditions for column chromatography were: 300˜400mesh silica gel powder as stationary phase, ethyl acetate (A) andpetroleum ether (B) as mobile phase, changing program of mobile phase(A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.44˜7.37 (m, 4H), 7.36˜7.29 (m, 4H),7.29˜7.26 (m, 1H), 7.24˜7.21 (m, 1H), 6.49 (d, J=15.7 Hz, 1H), 6.43˜6.35(m, 1H), 4.59 (d, J=8.4 Hz, 1H), 2.54˜2.39 (m, 2H), 1.63˜1.51 (m, 3H),1.37˜1.24 (m, 13H), 0.88 (t, J=6.8 Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-decyl (1,3-diphenylallyl) sulfoether(purity>95%); the product yield was calculated and the result was 79%.

Example 39 Synthesis of (E)-4-(1,3-diphenylallylthio) nitrile

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of4-chlorobutyronitrile (0.0621 g), 0.72 mmol of sodium thiosulfate(0.0988 g) and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) wereweighed and placed in 20 mL reaction tube. 1 ml water was added to thereaction tube as a solvent, and the tube was sealed. Reaction wascarried out with stirring at 80° C. for 5 hours. After completion of thereaction, the reaction solution was dried by ethyl acetate and anhydroussodium sulfate and separated by column chromatography, successively, toyield 0.0621 g of reaction product. Conditions for column chromatographywere: 300˜400 mesh silica gel powder as stationary phase, ethyl acetate(A) and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.42˜7.37 (m, 4H), 7.35˜7.26 (m, 5H),7.25˜7.22 (m, 1H), 6.52 (d, J=15.6 Hz, 1H), 6.42˜6.34 (m, 1H), 4.60 (d,J=8.7 Hz, 1H), 2.68˜2.53 (m, 2H), 2.49˜2.42 (m, 2H), 1.95˜1.86 (m, 2H)ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-4-(1,3-diphenylallylthio) nitrile(purity>95%); the product yield was calculated and the result was 71%.

Example 40 Synthesis of (E)-ethyl 4-(1,3-diphenylallyl thio) butyrate

0.3 mmol (E)-1,3-diphenylprop-2-enyl-1-ol (0.0631 g), 0.6 mmol of ethyl4-bromobutyrate (0.1170 g), 0.72 mmol of sodium thiosulfate (0.0988 g)and 0.06 mmol of tetrabutylammonium iodide (0.0222 g) were weighed andplaced in 20 mL reaction tube. 1 ml water was added to the reaction tubeas a solvent, and the tube was sealed. Reaction was carried out withstirring at 80° C. for 5 hours. After completion of the reaction, thereaction solution was dried by ethyl acetate and anhydrous sodiumsulfate and separated by column chromatography, successively, to yield0.0844 g of reaction product. Conditions for column chromatography were:300˜400 mesh silica gel powder as stationary phase, ethyl acetate (A)and petroleum ether (B) as mobile phase, changing program of mobilephase (A:B) from 1:20 to 1:6.

The reaction product was characterized and result was as follows:

¹H NMR (400 MHz, CDCl₃): δ=7.44˜7.39 (m, 3H), 7.38˜7.35 (m, 2H),7.34˜7.30 (m, 3H), 7.29˜7.26 (m, 1H), 7.24˜7.21 (m, 1H), 6.50 (d, J=15.6Hz, 1H), 6.42˜6.34 (m, 1H), 4.60 (d, J=8.7 Hz, 1H), 4.13˜4.06 (m, 2H),2.60˜2.45 (m, 2H), 2.44˜2.37 (m, 2H), 1.99˜1.85 (m, 2H), 1.22 (t, J=7.2Hz, 3H) ppm.

According to the characterization data, it can be seen that the reactionproduct was pure product of (E)-ethyl 4-(1,3-diphenylallyl thio)butyrate (purity>95%); the product yield was calculated and the resultwas 83%.

The foregoing is only preferred embodiments of the present application.It should be noted that several improvements and modifications may bemade by those ordinary skill in the art without departing from theprinciples of the invention, which should be regarded within theprotection scope of the present invention.

1. A method for synthesizing dissymmetric sulfoether, comprising: a)under the condition of tetrabutylammonium halide catalysis, compoundshaving a structure of formula (I), compounds having a structure offormula (II) and salts having sulfur and oxygen are reacted in a solventto give dissymmetric sulfoether having a structure of formula (III);

wherein, R1 is selected from phenyl, substituted phenyl, naphthyl,substituted naphthyl, thienyl or substituted thienyl; R2 is selectedfrom hydrogen, phenyl, substituted phenyl, naphthyl, substitutednaphthyl, thienyl or substituted thienyl; or R1, R2 form fluorene ringor thioxanthone ring with the C to which it is attached; R3 is selectedfrom hydrogen or alkyl; R4 is selected from hydrogen, phenyl,substituted phenyl, naphthyl, substituted naphthyl, thienyl orsubstituted thienyl; R5 is selected from hydrogen; or R4, R5 formfluorene ring or thioxanthone ring with the C to which it is attached;R6 is selected from alkyl or substituted alkyl; X is selected from Cl,Br or I; said salts having sulfur and oxygen include sodium thiosulfateand/or sodium sulfite.
 2. The method according to claim 1, wherein, R1is selected from phenyl, C1˜C5 alkyl-substituted phenyl, C1˜C5alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl,halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl,C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl; R2 isselected from hydrogen, phenyl, C1˜C5 alkyl-substituted phenyl, C1˜C5alkoxy-substituted phenyl, halogen-substituted phenyl, naphthyl, C1˜C5alkyl-substituted naphthyl, C1˜C5 alkoxy-substituted naphthyl,halogen-substituted naphthyl, thienyl, C1˜C5 alkyl-substituted thienyl,C1˜C5 alkoxy-substituted thienyl or halogen-substituted thienyl; R3 isselected from hydrogen and C1˜C5 alkyl; R4 is selected from hydrogen,phenyl, C1˜C5 alkyl-substituted phenyl, halogen-substituted phenyl,naphthyl, C1˜C5 alkyl-substituted naphthyl, halogen-substitutednaphthyl, thienyl, C1˜C5 alkyl-substituted thienyl orhalogen-substituted thienyl.
 3. The method according to claim 1, whereinsaid R6 is selected from C1˜C30 alkyl, cyano-substituted C1˜C20 alkyl,cyano-substituted C1˜C20 benzyl, C1˜C5 alkyl-substituted benzyl,halogen-substituted benzyl, fluorenyl and any of the structuralsubstituents represented in formulas (a-1)˜(a-9):

in formulas (a-3)˜(a-9), m₁, m₂, m₃, n, q, p₁, p₂, r₁, r₂ and e areinteger from 0 to 5, respectively.
 4. The method according to claim 1,wherein structural compound of formula (I) is1,1-diphenylpropyl-2-enyl-1-ol, 1,1-bis (4-fluorophenyl)prop-2-enyl-1-ol, 1,1-bis (4-chlorophenyl) prop-2-enyl-1-ol, 1,1-bis(4-bromophenyl) prop-2-enyl-1-ol, 1,1-bis (4-methylphenyl)prop-2-enyl-1-ol, 1,1-bis (4-methoxyphenyl) prop-2-enyl-1-ol,1-phenyl-1-p-methylphenyl-2-en-1-ol,1-(3,4-dimethylphenyl)-1-phenylprop-2-enyl-1-ol,1-phenyl-1-p-bromophenyl-2-enyl-1-ol,1-phenyl-1-o-fluorophenylprop-2-enyl-1-ol,1-(naphthalen-2-yl)-1-phenylprop-2-enyl-1-ol,2-methyl-1,1-diphenylprop-2-enyl-1-ol, 9-alkenyl-9H-fluorenyl-9-ol,9-alkenyl-9H-thioxanthen-9-ol, 1-phenylprop-2-enyl-1-ol,(E)-1,3-diphenylprop-2-enyl-1-ol, (E)-1,3-bis (4-fluorophenyl)prop-2-enyl-1-ol, (E)-1,3-bis (4-chlorophenyl) prop-2-enyl-1-ol,(E)-1,3-bis (4-bromophenyl) prop-2-enyl-1-ol, (E)-1,3-bis(naphthalen-2-yl) prop-2-enyl-1-ol, (E)-1,3-bis (thiophen-2-yl)prop-2-enyl-1-ol or (E)-2-methyl-1,3-diphenylprop-2-enyl-1-ol.
 5. Themethod according to claim 1, wherein structural compound of formula (II)is p-cyanobenzyl chloride, m-cyanobenzyl chloride,p-trifluoromethylbenzyl chloride, o-bromobenzyl chloride, p-methylbenzylbromide, 9-bromofluorene, (4-(chloromethyl) phenyl) (1H-indol-1-yl)methanone, ((3aR, 5S, 5aS, 8aS,8bR)-2,2,7,7-tetramethyltetrahydroxy-3aH-bis [1,3] dioxo [4,5-b:4′,5′-d] pyran-5-yl) methyl 4-(chloromethyl) phenyl ester,chloroacetonitrile, 1-bromoacetoacetate, 2-bromo-N,N-diethylpropionamide, bromopropyne, (3-chloropropyl-1-ynyl) benzene,ethyl 4-bromocrotonate, geranyl bromide, iodine iodobutane, and iodinen-decane, 4-chlorobutyronitrile or ethyl 4-bromobutyrate.
 6. The methodaccording to claim 1, wherein said molar ratio of structural compoundsof formula (I):structural compounds of formula (II):salts having sulfurand oxygen is 1:(1.5˜3):(2˜4).
 7. The method according to claim 1,wherein temperature of said reaction is 20˜90° C.
 8. The methodaccording to claim 1, wherein time of said reaction is 3˜8 h.
 9. Themethod according to claim 1, wherein in step a), after the completion ofreaction having structural compounds of formula (I), structuralcompounds of formula (II) and salts having sulfur and oxygen,extraction, drying and column chromatography are performed successivelyto give dissymmetric sulfoether having a structure represented informula (III).
 10. The method according to claim 1, wherein said solventis water.